Fabrication of patterned carbon nanotube thin films using electrophoretic deposition and ultrasonic radiation

A simple wet-deposition method for preparing patterned carbon nanotube (CNT) thin films is reported. Using electrophoretic deposition (EPD), CNTs were deposited over indium tin oxide (ITO) plates that had been patterned with a photoresist; consequently, CNTs covered not only the exposed ITO areas but also the photoresist areas because thinness of the photoresists could not prevent the transverse deposition of CNTs over the photoresist areas. The ultrasonic treatment for the samples removed only CNTs on the photoresist areas, resulting in the formation of patterned CNT thin films, because Ni metal formed during EPD connects CNTs to ITO plates.     

Continuous deposition of carbon nanotubes on a moving substrate by open-air laser-induced chemical vapor deposition

Continuous deposition of carbon nanotubes under open-air conditions on a moving fused quartz substrate is achieved by pyrolytic laser-induced chemical vapor deposition. A CO₂ laser is used to heat a traversing fused quartz rod covered with bimetallic nanoparticles. Pyrolysis of hydrocarbon precursor gas occurs and subsequently gives rise to rapid growth of a multi-wall carbon nanotube forest on the substrate surface. A “mushroom-like” nanotube pillar is observed, where a random orientation of carbon nanotubes is located at the top of the pillars while the growth is more aligned near the base. The typical carbon nanotube deposition rate achieved in this study is approximately 50 μm/s. At high power laser irradiation, various carbon microstructures are formed as a result of excessive formation of amorphous carbon on the substrate. High-resolution transmission and scanning electron microscopy, and X-ray energy-dispersive spectrometry are used to investigate the deposition rate, microstructure, and chemical composition of the deposited carbon nanotubes.     

Selective deposition of semiconducting single-walled carbon nanotubes onto amino-silane modified indium tin-oxide surface for the development of poly(3-hexylthiophene)/carbon-nanotube photovoltaic heterojunctions

A method is described to obtain separation of single-walled carbon nanotubes (SWCNTs) on an indium tin-oxide (ITO) substrate by modifying the conducting surface of ITO with amino-silane functional groups. Scanning electron microscopy confirmed that the amino-silane functionalization of the substrate is a critical parameter for the immobilization of separated nanotubes. In particular spin coating the SWCNT solution onto the amino-silane modified ITO surface results in a lower nanotube density with respect to the reference sample obtained on pure ITO together with the immobilization of semiconducting carbon nanotubes onto the substrate. The possibility of using these SWCNT thin films to obtain polymer/nanotube heterojunctions for the development of organic solar cells is considered.     

Towards type-selective carbon nanotube growth at low substrate temperature via photo-thermal chemical vapour deposition

Carbon nanotubes have been intensively researched for electronic applications, driven by their excellent electronic properties, where the goals are control and reproducibility of growth, semiconducting/metallic type selectivity and maintaining high quality of carbon nanotubes, in a process that is temperature-compatible with the electronics. Photo-thermal chemical vapour deposition can achieve these goals and, through a thorough investigation of the parameter space, we achieve very high nanotube-quality and growth rates, and produce a phase-diagram that reveals distinct regions for growing semiconducting and metallic single-walled nanotubes, as well as multi-walled. Correlation with the carbon-catalyst phase diagram allows for the development of a novel growth model. We propose that the temperature-gradient induces carbon diffusivity-gradient across the catalyst to yield the high growth rate. This is attributed to the increase of α-iron of catalyst. The growth control demonstrated here allows for integration of the nanotube growth process by photo-thermal deposition into mainstream electronics manufacture.     

Recent advances in hybrids of carbon nanotube network films and nanomaterials for their potential applications as transparent conducting films

The use of carbon nanotubes (CNTs) as transparent conducting films is one of the most promising aspects of CNT-based applications due to their high electrical conductivity, transparency, and flexibility. However, despite many efforts in this field, the conductivity of carbon nanotube network films at high transmittance is still not sufficient to replace the present electrodes, indium tin oxide (ITO), due to the contact resistances and semi-conducting nanotubes of the nanotube network films. Many studies have attempted to overcome such problems by the chemical doping and hybridization of conducting guest components by various methods, including acid treatment, deposition of metal nanoparticles, and the creation of a composite of conducting polymers. This review focuses on recent advances in surface-modified carbon nanotube networks for transparent conducting film applications. Fabrication methods will be described, and the stability of carbon nanotube network films prepared by various methods will be demonstrated.     

Energetic impact deposition of carbon nanotubes: Mechanism, nanopatterning, and field emission property

Carbon nanotube (CNT) films and nanopatterned lines were produced on silicon and indium tin oxide (ITO) substrates using energetic impact deposition (EID) of CNT aerosols. With sufficient impact energy, CNTs can be directly bound on the substrate without any polymer binder, catalyst, or chemical treatment. Field emission data indicates that the deposited CNTs with a form of many terminal protuberances play a role of electron field emitter. The mechanism of deposition process and interfacial chemical bond formation were also investigated by classical molecular dynamics simulation.     

Selective growth of diamond and carbon nanostructures by hot filament chemical vapor deposition

Diamond and carbon nanostructures have been synthesized selectively on differently pretreated silicon substrates by hot filament chemical vapor deposition in a CH₄/H₂ gas mixture. Under typical conditions for CVD diamond deposition, carbon nanotube and diamond films have been selectively grown on nickel coated and diamond powder scratched silicon surface, respectively. By initiating a DC glow discharge between the filament and the substrate holder (cathode), well aligned carbon nanotube and nanocone films have been selectively synthesized on nickel coated and uncoated silicon substrates, respectively. By patterning the nickel film on silicon substrate, pattern growth of diamond and nanotubes has been successfully achieved.     

Direct growth of vertically aligned carbon nanotubes on a planar carbon substrate by thermal chemical vapour deposition

Uniform, vertically aligned multiwalled carbon nanotube arrays (VACNTs) were grown on glassy carbon-like thin films by thermal chemical vapour deposition (CVD). Thin (5 nm) aluminum and iron catalyst layers were pre-deposited by evaporation on the carbon substrates and VACNTs were grown at 750 °C by water-assisted CVD using ethylene as the carbon source. The aluminum layer was shown to be essential for aligned nanotube growth. VACNT arrays adhered strongly to the carbon film with low contact resistance between the VACNTs and the substrate. The VACNT arrays grown directly on the planar conducting carbon substrate have attractive properties for use as electrodes. Excellent voltammetric characteristics are demonstrated after insulating the arrays with a dielectric material.     

The formation of stacked-cup carbon nanotubes using chemical vapor deposition from ethanol over silica

Processes involved in using SiO₂ particles as catalysts for stacked-cup carbon nanotube formation in a spray pyrolysis chemical deposition method from ethanol were investigated. In addition, the recyclability of the SiO₂ substrates is investigated. The SiO₂ particles are shown to reduce to SiC. Moreover, the addition of triethylborate to produce boron species, and extended reactions, through recycling, leads to higher yields by improving the availability of SiC species. The formation of the carbon nanostructures is best explained through a carbon dissolution mechanism.     

Optimization of methane cold wall chemical vapor deposition for the production of single walled carbon nanotubes and devices

Carbon nanotubes are synthesized by cold wall chemical vapor deposition (CVD) using methane as the carbon source and iron thin film catalyst. The yield of thin nanotubes as determined by scanning electron microscopy (SEM) is strongly dependent on the precise CVD process and the preparation of the substrate. The effects of pressure (5–80 kPa), temperature (700–950 °C), substrate conditioning (air preheat) and metallization (Fe, Al, Mo) on thin nanotube yield are reported. High yields of thin nanotubes are obtained under optimum conditions. These thin nanotubes are candidates to be single walled carbon nanotubes (SWNTs) and Raman spectroscopy, photoluminescence spectroscopy and electrical transport provide evidence that, at least at optimum conditions, many, and perhaps all of the thin nanotubes are single walled. Single nanotube field effect transistors are fabricated and factors affecting device yield are reported. Optimum single nanotube device yield does not necessarily coincide with the optimum nanotube yield.     

Synthesis of diamond hexagonal nanoplatelets by microwave plasma chemical vapor deposition

Variation of diamond deposition with temperature gradient was studied using standing-up substrates embedded within the plasma ball in microwave plasma chemical vapor deposition (MPCVD). The substrate is a polycrystalline diamond coated with a 30-nm thick iron film before deposition. Surface morphologies of the deposits and their crystalline characteristics were characterized by scanning electron microscopy, transmission electron microscopy (TEM), and selected area diffraction. On the upper area of the specimen near the center of the plasma ball where the temperature is the highest (>1100 °C), formation of diamond nanoplatelets in hexagonal shape with a thickness of 20–60 nm and side length of several hundreds of nanometers is found. In the middle region, diamond nanoplatelets with some iron nanoparticles are observed. Around the bottom region with low temperature near the edge of the plasma ball, nanodiamonds, Fe nanoparticles, and carbon nanotubes coexisted. The relative temperature distributions of diamond and carbon nanotube growth are briefly discussed.     

Performance of nanotube-based electrodes from temperature-controlled electrophoretic deposition

Single-walled carbon nanotube-coated electrodes were fabricated from functionalized nanotube aqueous suspensions by the electrophoretic deposition (EPD) method for a potential large-scale production of nanostructured electrical components. The dependences of nanotube coatings and their electrochemical properties on the processing temperature of EPD were investigated. Optical and scanning electron microscope images were used to examine the microstructure, surface roughness, and thickness of the nanotube-based electrodes. The BET-specific surface area and the average pore size were analyzed. The prepared electrodes were characterized by cyclic voltammetry and their specific capacitances were measured. Correlations between the processing temperature and the electrode capacitance, nanotube loading, specific surface area, and average pore size were experimentally characterized.     

Chemical vapour deposition of pyrolytic carbon on carbon nanotubes: Part 3: Growth mechanisms

As a first step to identify the growth mechanism of various pyrolytic carbon deposit morphologies onto multiwall carbon nanotubes (MWNTs) presented in earlier papers, we determined their growth chronology by carrying-out synthesis experiments involving a large time range. We propose that the formation of any of the deposit morphologies is the consequence of the primary formation of hydrocarbon liquid droplets in the gas phase and their subsequent deposition onto the MWNTs. This makes the formation mechanisms of the various deposit morphologies depend on physical phenomena related to the wetting of nanotube surfaces by the droplets, where the [droplet diameter]/[nanotube diameter] ratio plays an important role. The droplets are the result of the recombination of species issued from the cracking of the gaseous precursor (methane), and their characteristics (number, size, and aromaticity) depend on experimental parameters such as temperature, time of flight, and gas phase composition. The results bring a new light to the currently admitted hypotheses for the mechanisms of pyrolytic carbon deposition, and revitalise the liquid droplet theory formerly proposed by Grisdale in the 1950s, at least in the range of conditions investigated.     

Control of the single-wall carbon nanotube mean diameter in sulphur promoted aerosol-assisted chemical vapour deposition

The influence of gas flow on nanotube diameter during the synthesis of high-purity, very long single-wall carbon nanotubes (SWCNT) via aerosol-assisted chemical vapour deposition is reported. The sample morphology, nanotube yield, defect concentration and amount of carbonaceous impurities, as well as the mean diameter and the diameter distribution of the SWCNTs were analysed by combined scanning- and transmission electron microscopy, Fourier Transform Raman spectroscopy and optical absorption spectroscopy. The results show that by using a solution of ferrocene and sulphur in m-xylene the addition of sulphur as a promoter was found to enhance the SWCNT growth and to increase the yield. A reduction of the mean diameter and a change in the diameter distribution are observed when the total gas flow is increased.     

Selective growth of CNT by using triode-type radio frequency plasma chemical vapor deposition method

Triode-type radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) equipment has been used in order to grow well-aligned carbon nanotubes on Si and glass substrates below 600 °C. This CVD equipment allows the growth of a well-aligned carbon nanotube with an inside and an outside diameter of 7 and 17 nm, respectively. The selective growth of the CNT was demonstrated.     

Horizontally aligned carbon nanotube field emitters fabricated on ITO glass substrates

Horizontally aligned carbon nanotube (CNT) field emitters, in which electrons are emitted from the side of CNTs, are fabricated on indium tin oxide (ITO) glass substrates by electrophoretic deposition and fissure formation techniques. A thin film of CNTs is deposited onto an ITO glass plate using an aqueous mixture of CNTs and the cationic detergent cetyltrimethylammonium bromide by applying a negative voltage to the ITO glass plate. Then, an additional layer of sodium dodecyl sulfate (SDS), an anionic detergent, is deposited on the CNT film. This is done using an aqueous solution of SDS by applying a positive voltage. Through the process of firing, CNTs with a clean surface are exposed in the fissures produced. No further treatment is needed to initiate or augment field emission. The CNT field emitters show relatively good field-emission properties such as high current density (11 mA/cm² at an applied electric field of 4.3 V/μm), low turn-on field (2.2 V/μm), and good stability (98 h for 10% degradation of current density from 400 μA/cm²).     

Self-assembling of multi-walled carbon nanotubes on a porous carbon surface by catalyst-free chemical vapor deposition

Synthesis of carbon nanotubes (CNTs) by catalyst-free chemical vapor deposition (CFCVD) is one of the most important challenges in nanotube science. Self-assembling multi-walled CNTs (MWCNTs) were produced on a porous carbon surface using carbon black (CB) as a substrate, at 800 °C by the decomposition of diluted ethylene. MWCNTs with an outer-diameter distribution of 20–80 nm, examined by scanning and transmission electron microscopy, could be self-assembled on pore structures of CB surface by CFCVD.     

Direct growth of MWCNTs on 316 stainless steel by chemical vapor deposition: Effect of surface nano-features on CNT growth and structure

Multi-walled carbon nanotubes were directly grown by chemical vapor deposition on as-received or pretreated 316 SS without application of an external catalyst. A detailed study of the size distribution of surface features formed by different steps of the synthesis process showed that the heating cycle and any complementary pretreatment may produce significant changes of the surface topography, thus suggesting that the influence of any primary characteristics of the original surface, as well as those caused by a pretreatment, should be assessed in conjunction with the effects of heating. Average lateral size of nano-features less than 60 nm (after heating) were shown to favor mainly the carbon nanotube growth while a larger features size was associated predominantly to the carbon nanofiber synthesis. Scanning and transmission electron microscopy observations suggest two different mechanisms for nanotube/nanofiber growth: (1) base growth mode caused by nanosized hills on the surface catalyzing the nanotube/nanofiber synthesis, (2) tip growth mode requiring substrate surface break-up as a preliminary step to form catalytic particles, with similarities to the “metal dusting” mechanisms. While untreated steel showed the best results concerning carbon nanotube coverage and homogeneity, oxidized-reduced samples showed an almost exclusive growth of carbon nanofibers with a full coverage.     

Prospective growth region for chemical vapor deposition synthesis of carbon nanotube on C–H–O ternary diagram

Chemical vapor deposition has become a standard process for synthesizing carbon nanotubes. Since the successful use of chemical vapor deposition for the first time, much effort has been expended into exploring various carbon sources that can be used to synthesize carbon nanotubes, such as methane, ethane, and ethanol. However, whole perspectives for suitable carbon sources have not been clear. In this study, we performed experiments in order to determine that the appropriate C–H–O components ratio in raw materials can be used to synthesize carbon nanotubes. We also examined a variety of raw materials in our newly developed round-trip-type vacuum furnace in order to determine whether they could be used to synthesize a carbon nanotube. We used Raman spectroscopy to identify the developed carbon nanotube, and we plotted the component ratios of effective and ineffective materials on a C–H–O ternary diagram; in this diagram, the growth region became highly apparent. It should be noted that for the growth of the carbon nanotube, this region should satisfy the equation O < C < (H + O) in molar ratio. Furthermore, it was observed that adjusting the component ratios by mixing raw materials did not cause an inconsistency in the growth region.     

Current understanding of the growth of carbon nanotubes in catalytic chemical vapour deposition

Due to its higher degree of control and its scalability, catalytic chemical vapour deposition is now the prevailing synthesis method of carbon nanotubes. Catalytic chemical vapour deposition implies the catalytic conversion of a gaseous precursor into a solid material at the surface of reactive particles or of a continuous catalyst film acting as a template for the growing material. Significant progress has been made in the field of nanotube synthesis by this method although nanotube samples still generally suffer from a lack of structural control. This illustrates the fact that numerous aspects of the growth mechanism remain ill-understood. The first part of this review is dedicated to a summary of the general background useful for beginners in the field. This background relates to the carbon precursors, the catalyst nanoparticles, their interaction with carbonaceous compounds and their environment. The second part provides an updated review of the influence of the synthesis parameters on the features of nanotube samples: diameters, chirality, metal/semiconductor ratio, length, defect density and catalyst yield. The third part is devoted to important and still open questions, such as the mechanism of nanotube nucleation and the chiral selectivity, and to the hypotheses currently proposed to answer them.